PT101695B - DYES WITH REAGENTS WITH FIBERS - Google Patents

Abstract

Fibre-reactive disazo dyes correspond to formula 1, <IMAGE> wherein the symbols are defined as in claim 1, and they are present as free acids or in salt form. They are used as reactive dyes for dyeing or printing hydroxy-group-containing or nitrogen-containing organic substrates, especially leather or fibrous material, which consists of or contains natural or synthetic polyamides or natural or regenerated cellulose. The dyeings obtained have high fixation values and good light fastness.

Description

DESCRIPTION

The invention relates to disazo dyes reactive with fibers, processes for their production and their use as reactive dyes in dyeing and printing processes.

The objects of the invention are composed of the formula I

and its salts, in which

Q indicates hydrogen, C ₁ ~ C ₄ alkyl, -CH ₂ SO ₃ H or -COOH,

Q ₂ indicates hydrogen, -CN, -CONH ₂ or -CH ₂ SO ₃ H,

Q ₃ indicates hydrogen, ^C ₁ ~ C ₄ alkyl or ^C 4 ^-C 4 substituted alkyl, each R group, independently of each other, indicates hydrogen or ^{C 1 -C} 4 alkyl, or together form a ^C x ^- bridge ^C 4 alkylene,

X indicates an aliphatic or aromatic bonding member and Hal indicates chlorine or fluorine, and the carbonyl carbon atom of the -CONH- group is attached to the phenyl radical at the 3 or 4 position.

In a compound of formula I, each alkyl or alkylene group can be straight or branched and can be substituted with a hydroxyl group. In a hydroxy-substituted alkyl or alkylene group, which is bonded to nitrogen, the hydroxy group is preferably bonded to a C atom which is not bonded directly to nitrogen.

preferably means methyl, -CH ₂ SO ₃ H or COOH, more preferably methyl.

Q ₂ preferably means -CH ₂ SO ₃ H.

Q ₃ preferably means hydrogen, methyl or ethyl, or methyl or ethyl carrying a sulfonic acid radical substituent, more preferably Q ₃ represents an ethyl group.

Each R group is preferably expressed by hydrogen, -CH ₃ , or both R groups together signify an ethylene bridge.

X preferably signifies a bridge ^c 2_3 straight chain or branched alkylene, a straight chain bridge ^c 2_3 alkylene or branched carrying a hydroxy substituent a phenylene bridge , or a phenylene bridge carrying a methyl substituent or a sulfonic acid moiety, more preferably X means a 1,2-propylene group.

Hal preferably means chlorine.

carbonyl carbon atom of the -CONH group is preferably attached to the phenyl radical at position 4.

Preferred compounds are according to formula Ia

-N-X-N

R _to R

CONH

and its salts, in which

Q. indicates methyl, -CH SO H or COOH,

2nd

Q_ indicates -CH SO H,

Z 3. Z J

Q _3a indicates hydrogen, methyl or ethyl, or methyl or ethyl carrying a sulfonic acid substituent.

R indicates hydrogen, methyl or both R together with a indicates an ethylene bridge,

X indicates a straight-chain or branched C-C * alkylene bridge, a ^C ₂ ^-C 3 alkylene bridge carrying a hydroxy substituent, a phenylene bridge, or a phenylene bridge carrying a methyl substituent or sulfonic acid radical, and

Hal _a means chlorine, and the carbonyl carbon atom of the -CONH- group is attached to the phenyl radical at position 3 or 4, preferably at position 4.

A particularly preferred compound according to the invention has the formula ch ₃

-nh-ch-ch ₂ -nh

Cl

I

When compounds of formula I are present in the form of salt, the constitution of the cation of the sulfonate groups and any carboxylate groups that may be present is not a vital factor, but it can be any non-chromophoric cation conventional in reactive dye chemistry as long as the corresponding salts satisfy the water solubility requirements.

Examples of suitable cations are unsubstituted or substituted metal, alkali or ammonium ions, for example lithium, sodium, potassium, ammonium, mono-, di-, trie tetramethylammonium, triethylammonium and mono-, di- and triethanolammonium.

Preferred cations are the alkali metal ions and the ammonium cation, of which sodium is the particularly preferred cation.

The cations of the sulfonate groups and any carboxylate groups in compounds of the formula I when in their salt form can be the same or different and represent a mixture of the aforementioned cations, i.e. the compounds can exist in a mixed salt form.

the invention provides in another aspect a process for the formation of compounds according to formula I comprising the reaction of a compound of formula II

Hal with a compound of formula III

HN-X-NH where Q, Q ₂ , Q ₃ , R, X and Hal are as defined above.

The reaction is preferably carried out in an aqueous medium. The reaction medium is maintained under basic conditions, preferably with a pH ranging between 8 and 8.5. The reaction temperature varies between 20 and 60 ° C and is preferably carried out at a temperature ranging between 35 and 45 ° C, more preferably at 40 ° C.

Compounds of formula II are obtained, for example, when a compound of formula IV

H

IV is diazotized and coupled to a coupling component of formula V

HO N O

so the compound of the formula h ₃ cconh

CONH

is obtained, then the acetyl group is cleaved under acidic conditions ie with 3 to 6% hydrochloric acid at a temperature ranging between 75 ° C and 95 ° C preferably 80 ° C and the obtained compound is condensed with cyanuric halide in a aqueous medium, preferably having a pH of 4 to 7 and at a temperature between 0 ° C and 5 ° C in order to form the compound of the formula

II.

The isolation of the compounds of the formula I can take place in a known manner, for example, the compounds can be separated from the reaction mixture by treatment with conventional salt with alkali metal salts before filtration and drying, optionally under vacuum at a temperature slightly elevated.

Depending on the reaction and isolation conditions, a compound of formula I is obtained in the form of a free acid or preferably in the form of a salt or a mixed salt, in which case it contains, for example, one or more of the cations mentioned above. However, mixed salts or salts can also be produced from the free acid in a manner that is conventional per se, and vice versa, or a conventional salt transformation can be carried out.

The compounds of formulas III to V are either known starting materials or can be obtained by using

conventional syntheses from known starting compounds.

The compounds of the formula

I, its salts and mixtures are reactive dyes and are suitable for dyeing or printing organic substrates containing hydroxy group or containing nitrogen.

Consequently, in another aspect of the invention there is provided a process for dyeing or printing organic substrates containing hydroxy group or containing nitrogen in which the dyeing is carried out with compounds previously defined herein, their salts or mixtures thereof.

It should be understood that any reference made previously or here after to compounds or salts in the plural is also reference to compound or salt in the singular.

Preferred substrates are leather and fibrous materials that consist of or contain natural or synthetic polyamides and in particular natural or regenerated cellulose, such as cotton, viscose or artificial rayon fiber. The substrate that is usually preferred is textile material consisting of or containing cotton.

In yet another aspect of the invention there is provided the use of compounds defined hereinbefore, their salts or mixtures thereof for dyeing or printing substrates previously described herein.

The compounds of formula I can be used in dye baths or in printing pastes according to all dyeing or printing processes that are conventional for reactive dyes. Dyeing is preferably carried out by the discharge process at a temperature ranging between 80 ° C and 100 ° C.

The compounds according to the invention and their salts can be used as individual dyes or as mixtures of compounds, mixtures of salts or mixtures of compounds and salts. In addition, in view of its good compatibility with certain other reactive dyestuffs, their salts or mixtures may form part of a combination of the dye composition with certain other reactive dyestuffs of the same class, certain other dyestuffs that have dye properties comparable, for example all values of overall stability and discharge, with those of the compounds and salts of the invention.

In another aspect of the invention there is provided an organic substrate containing hydroxy or containing nitrogen dyed or printed according to a dyeing or printing process described above.

Good discharge and fixation values are obtained with the compounds of formula I. The unsecured part of the dye can be quickly removed. The dyeings and prints obtained have good stability in relation to light and also good stability in relation to light with humidity. In addition, they have good stability properties in relation to moisture, for example with washing, water, sea water and perspiration, and they have good resistance to oxidative influences such as chlorine-containing water, hypochlorite bleaches, bleaches with peroxide and detergents containing perborate.

The following examples serve to illustrate the invention. In the examples, the parts are by weight or by volume and the percentages are by weight or by volume; temperatures are given in degrees celsius.

Example 1

A solution of 61.5 parts of acid

3-amino-1- (aminobenzoylamino) -benzene-4-sulfonic in 700 parts of water was brought to pH 6 with 14.5 parts of 30% hydrochloric acid. 27.5 parts of acetic anhydride were added dropwise over the course of 2 hours with the pH remaining between 5.9 and 6.1. The pH value is hereby maintained with 150 parts of 15% lithium hydroxide. During the reaction, the temperature was maintained between 10 and 15 ° C. Then the pH was adjusted to 4.0 with 32 parts of 30% hydrochloric acid, and the product was salified with 150 parts of sodium chloride. The solution was filtered giving a precipitate of compound A (61 parts)

69.8 parts of compound A in 600 parts of water were mixed with 63 parts of 30% hydrochloric acid, and

13.8 parts of a 4N sodium nitrite solution. After neutralizing the excess nitrite with sulfaminic acid, 58 parts of 1-ethyl-5-carbampoyl-6-hydroxy-4-methyl-3-sulfomethylpyridone were added to the solution and the pH was adjusted to 5.0 with 90 parts of solution of 15% sodium hydroxide. A cloudy solution of compound B was obtained, with the following formula:

h ₃ council

CONH

The compound B solution was mixed with 260 parts of 30% hydrochloric acid and stirred for 4 hours at

80 ° C. A yellow precipitate of compound C of the following formula was filtered off at 25 ° C.

ch ₂ ch ₃

135 parts of compound C were suspended in 400 parts of water. 37 parts of cyanuric chloride, which were stirred in 200 parts of ice and 80 parts of water for 20 minutes, were added to the suspension for 20 minutes. During this time, the temperature was maintained between 0 and 5 ° C with an ice bath, and the pH was maintained between 4.0 and 6.0 with 125 parts of 15% sodium hydroxide. After 1-5 hours, condensation was complete, and a cloudy yellow solution of the dichlorotriazine dye material of the formula was obtained

CONH

The cloudy solution of the dichlorotriazine dye material was adjusted to pH 7.0 with 4 parts of 15% lithium hydroxide solution and heated to 40 ° C. Then, 8 parts of 1,2-diaminopropane were added dropwise over 30 minutes with a pH ranging between 8.0 and 8.5. After 2-3 hours with a pH ranging between 8.0 and 8.5, condensation was complete. In the course of the reaction, 100 parts of 15% lithium hydroxide solution were used in order to maintain the pH value. The dichlorotriazine dye material was salified with 190 parts of sodium chloride at 50-60 ° C, filtered off and dried. 228 parts of dichlorotriazine yellow dye material of the formula

Cl

I ch ₃

-nh-ch-ch ₂ -nh

were obtained with a 422nm lambda (water).

The pretenses and prints made with this cotton dye material by the usual method were greenish yellow. They were notable for their good light stability, resistance to oxidative influences, and good fixation values.

Examples 2-13

Other compounds of formula I were produced in a manner analogous to the method described in Example 1, using corresponding starting materials. These are indicated in the Table below.

Hal

I

Ξχ. Ν'-Χ-Μ- Hai D / ’m Q. * ç, Zmax (H, O) 2 -HNCH.CH.NH- ç P C'r ₃ -H -CHjCHjSO, - 424 3 -HNCH ₂ CH ₂ NH- Ç: n CH, CH.SO.H • CHjCH, 420 4 CH, I ' -HNCH.CHNH- r * i m -CH, SO, H -KNOW, -CH, 425 I HM -,. - NH- r 0 C ^U ₃ -CHjSCjH -CH.CH, 423 6 -HNCH ₂ CH (OH) CH ₂ NH- m -COOH -H -H 420 7 ch, -HNCHCHjNH- F m -CH, -CH ₂ SO, H -CHjCH, 424 8 ,, NH- Ç' P -CH, -KNOW, -ch, ch „sc, h 42i 9 -HNCH, CH _2. \ H- r 'i P -Cr !, SO, H -CN -CHjCH, 423 10 CH, -HNCHCHjNH- Ç: m -CH, -CH ₂ SO, H CH, 427 i

Ξχ. _ Μ-Χ-Ν- R R Η al Ρ / ΓΓΊ G. Q. q ₃ Àrnax (H, 0) 1 1 -ΗΝ —-- ΝΗ- '~ so ₃ h Ρ -COOH -Η -Η 419 j I 2 ηΓ ·. '’· —ΝΗ- Ρ -C.Ç -ch _{2 to 3} h .ru cw - 1 _<2 <z. .5 424 13 ί \ - Ν Ν- \ / Ρ -CH, -ch _{2 to 3} h -CH, CH ₃ 422

Dyeing examples for hot and cold staining

The following examples illustrate the possibilities for using the coloring materials described. Coloring materials containing chlorine are applied according to Application Example A and coloring materials containing fluorine according to Application Example B

Application Example A

A dye bath consisting of 1,000 parts of demineralized water, 80 parts of Glauber (calcined) salt, 1 part of sodium salt of l-nitrobenzene-3-sulfonic acid and 1 part of the coloring material of Example 1 was heated to 80 ° C over 10 minutes. Then, 100 parts of mercerized cotton were immersed in the resulting solution. Staining was carried out at 80 ° C for 5 minutes before the solution was raised to 95 ° C for 15 minutes. After 10 minutes at 95 ° C, 3 parts of soda were added, followed by another 7 parts of soda after 20 minutes, and another 10 parts of soda after 30 minutes at 95 ° C. Dyeing was subsequently continued for 60 minutes at 95 ° C. The dyed material was then removed from the dyebath, and rinsed for 2 minutes with running demineralized water at 60 ° C ± 10 ° C and for 1 minute with tap water at 60 ° C ± 10 ° C. The material was then washed twice for 10 minutes, each time in 5,000 parts of boiling demineralized water, and subsequently rinsed for 2 minutes with running demineralized water at 60 ° C ± 10 ° C, 1 minute with running tap water. at 60 ° C ± 10 ° C and 1 minute with cold tap water. After drying, a good color of the bright greenish yellow cotton with good stability was obtained.

Application Example B

A dye bath consisting of 1,000 parts of

demineralized water, 80 parts of Glauber salt (calcined) and 1 part of dye material of Example 2 was heated to 50 ° C over 10 minutes. Then, 100 parts of mercerized cotton were dipped in the resulting solution. After 25 minutes at 50 ° C, 0.7 parts of soda were added, followed by an additional 1.3 parts of soda after 20 minutes, and another 2 parts of soda after 30 minutes at 50 ° C. The bath was subsequently heated over 15 minutes at 60 ° C, and the dyeing continued for 60 minutes at 60 ° C. The dye material was then removed from the dye bath, and rinsed with running demineralized water at 60 ° C ± 10 ° C and for 1 minute with running tap water at 60 ° C ± 10 ° C. The dye material was then washed twice for 10 minutes, each time in 5,000 parts of boiling demineralized water, and subsequently rinsed for 2 minutes with running demineralized water at 60 ° C ± 10 ° C, 1 minute with running water. piped at 60 ° C ± 10 ° C and 1 minute with cold tap water. After drying, a bright greenish yellow dyeing with good stability was obtained.

The dyestuffs of Examples 3 to 13 or mixtures of dyestuffs of Examples 1 to 13 were used to dye cotton in a manner analogous to that described in Examples A and B. Dyes of bright yellow color were obtained, which showed good drying properties. stability.

Application Example C

A printing paste having the components part of the dye material of example 1

100 pieces of urea

330 parts of water

500 parts of a 4% sodium alginate thickening agent 10 parts of the sodium salt of 1-nitrobenzene acid no-3-sulfonic 20 soda pieces 000 parts in all

was applied to the cotton material by means of conventional printing processes. The stamped and dried material was subjected to steam for 4-8 minutes at 102-105 ° C before being passed through cold water and hot water. The fixed cotton material was subsequently washed at the boiling point (in a manner similar to that of Example A) and dried. The yellow-green print obtained showed good properties of overall stability.

The dyestuffs of examples 2 to 13 were also used for printing cotton in a manner analogous to the method of example C. In all cases, prints of bright yellow color with good stability properties were obtained.

Lisbon, May 4, 1995

JORGE CRUZ

Official Industrial Property Agent

VICTOR CORDON STREET, 10 - A 3 *

Claims (9)

Reactive diazo dye compounds with characterized by presenting the formula and its salts, in which Q ₁ indicates hydrogen, C ₁ -C ₄ alkyl, -CH ^ SO ^ H or -COOH, Q indicates hydrogen, -CN, -CONH_ or -CH S0 _o H, Q ₃ indicates hydrogen, ^c 1 - ^c 4 alkyl or substituted alkyl, each group R, independently of one another, indicates hydrogen or C-C alkyl, or together form a C-C bridge. alkylene, X indicates an aliphatic or aromatic bonding member and Hal indicates chlorine or fluorine, and the carbonyl carbon atom of the -CONH- group is attached to the phenyl radical at the 3 or 4 position. 2. Compounds according to claim 1, characterized in that they correspond to formula Ia and its salts, in which i Q indicates methyl, -CH SO H or COOH, laz 3 Q indicates -CH SO H, z az 3 Q indicates hydrogen, methyl or ethyl, or methyl or ethyl z a carrying a sulfonic acid radical substituent. R indicates hydrogen, methyl or both R together aa indicates an ethylene bridge, X indicates a straight or branched chain C-C alkylene bridge, a C ^-C ^ alkylene bridge carrying a hydroxy substituent, a phenylene bridge, or a phenylene bridge carrying a methyl substituent or sulfonic acid radical, and Hal _a means chlorine,) and the carbonyl carbon atom of the -CONH- group is attached to the phenyl radical in the 3 or 4 position, preferably in the 4 position. Compound according to either claim 1 or claim 2, characterized in that it has the formula 4. CONH Process for the production of compounds of formula I, characterized by comprising the step of reacting a compound of formula II II with a compound of formula III HN-X-NH III where Q, Q, Q4, R, X and Hal are as defined hereinbefore. 5. Process for dyeing or printing organic substrates containing hydroxy groups or containing nitrogen, characterized in that the dyeing or printing is carried out with compounds according to any one of claims 1 to 3, their salts or mixtures thereof. Process according to claim 5, characterized in that it is intended for the dyeing or printing of leather or fibrous materials, which consist of or contain natural or synthetic polyamides or regenerated cellulose. Process according to either of claims 5 or 6, characterized in that it is intended for dyeing or printing textile material, which consists of or contains cotton. 8. Substrates containing hydroxy groups or containing nitrogen, characterized in that they are dyed or printed according to any one of claims 5 to 7. Use of compounds according to any one of claims 1 to 3, their salts or mixtures thereof, characterized in that said compounds are used in the dyeing or printing of substrates containing hydroxy groups or containing nitrogen.